N-type conjugated compounds containing diborylene units, methods of making, and a device comprising the compound

Abstract

N-type conjugated compounds are disclosed which include at least one conjugated electron-acceptor unit The conjugated electron-acceptor unit includes a diborylene unit. The compounds find application in an electron acceptor layer of an electronic device.

The invention claimed is: 
     
       1. A n-type conjugated polymer comprising:
 at least one conjugated electron-acceptor unit, the at least one conjugated electron-acceptor unit comprising a cyclic diborylene unit, and an optional π-conjugated linker unit. 
 
     
     
       2. The n-type conjugated polymer of  claim 1 , wherein the cyclic diborylene unit includes two boron atoms in a same at least five membered ring. 
     
     
       3. The n-type conjugated polymer of  claim 2 , wherein the diborylene unit has the general structure represented by Structure 2: 
       
         
           
           
               
               
           
         
         wherein B is a boron atom, X and Y are independently selected from a u-conjugated group and a p-conjugated atom. 
       
     
     
       4. The n-type conjugated polymer of  claim 3 , wherein Y is a p-conjugated atom and is selected from S, O and N—R 0 ,
 wherein R 0  is selected from H, alkyl, aromatic and heterocyclic groups, and substituted derivatives and combinations thereof. 
 
     
     
       5. The n-type conjugated polymer of  claim 2 , wherein Y is O. 
     
     
       6. The n-type conjugated polymer of  claim 2 , wherein at least Y is a π-conjugated group selected from fused rings and vinyl groups. 
     
     
       7. The n-type conjugated polymer of  claim 1 , wherein said diborylene unit has any of the structures represented by Structures 3, 4, 5, 8, and 9 and combinations thereof: 
       
         
           
           
               
               
           
         
         wherein Y is selected from S, O and N—R 0  and wherein R 0  is selected from H, an alkyl group, an aromatic hydrocarbon group, or a heterocyclic group and substituted derivatives and combinations thereof. 
       
     
     
       8. The n-type conjugated polymer of  claim 1 , wherein the at least one diborylene unit comprises a plurality of diborylene units and electron acceptor unit further comprises at least one linkage unit which spaces first and second of the diborylene units. 
     
     
       9. The n-type conjugated polymer of  claim 1 , wherein the polymer comprises the general structure 11: 
       
         
           
           
               
               
           
         
         where A is the diborylene unit, L is the linkage unit, and n>1, x≧1, and y≧0. 
       
     
     
       10. The n-type conjugated polymer of  claim 9 , wherein the linkage unit L comprises at least one of a conjugated C 3 -C 30  alkyl group, and a C 6 -C 30  aromatic or heteroaromatic group. 
     
     
       11. The n-type conjugated polymer of  claim 9 , wherein the linkage unit L comprises any of the structures represented by Structures 12, 13, 14, 15, 43 and 44: 
       
         
           
           
               
               
           
         
       
     
     
       12. The n-type conjugated polymer of  claim 9 , wherein n≧10. 
     
     
       13. The n-type conjugated polymer of  claim 9 , wherein the polymer comprises at least one of Structures 16, 17, 18, 19, 20, and 21: 
       
         
           
           
               
               
           
         
       
     
     
       14. The n-type conjugated polymer of  claim 1 , further comprising at least one conjugated electron-donor unit. 
     
     
       15. The n-type conjugated polymer of  claim 14 , wherein said at least one conjugated electron-donor unit comprises any of the structures represented by Structures 23, 24, and 25: 
       
         
           
           
               
               
           
         
       
     
     
       16. The n-type conjugated polymer of  claim 1 , wherein the diborylene units are spaced from the at least one conjugated electron-donor unit by a spacer unit. 
     
     
       17. The n-type conjugated polymer of  claim 16 , where the spacer unit is represented by C t H 2t+1 , and wherein t≧0. 
     
     
       18. The n-type conjugated polymer of  claim 1 , wherein the polymer has a general structure represented by Structure 25: 
       
         
           
           
               
               
           
         
         wherein A is the diborylene unit; 
         L is a conjugated linkage unit; 
         C is an optional non-conjugated spacer unit; 
         D is at least a repeat conjugated electron-donor unit;
 x is ≧1; 
 y is ≧0; 
 w is ≧0; 
 z is ≧1; and 
 n is ≧1. 
 
       
     
     
       19. The polymer of  claim 18 , wherein z is ≧10. 
     
     
       20. The polymer of  claim 18 , wherein x=1 and y=1. 
     
     
       21. The polymer of  claim 18 , wherein n≧10. 
     
     
       22. An electronic device comprising a layer of the n-type conjugated polymer of  claim 1 . 
     
     
       23. The electronic device of  claim 22 , wherein said electronic device is one of an organic photovoltaic device (OPV), an organic light emitting diode (OLED), and an organic field effect transistor (OFET). 
     
     
       24. A method of forming an n-type conjugated polymer comprising polymerizing a monomer unit having the general structure: 
       
         
           
           
               
               
           
         
         wherein each G is independently a hydrogen or halide, and each X and Y is a π-conjugated group or p-conjugated atom. 
       
     
     
       25. The method of  claim 24 , wherein the n-type conjugated polymer comprises:
 at least one conjugated electron-acceptor unit, the at least one conjugated electron-acceptor unit comprising a cyclic diborylene unit, and an optional u-conjugated linker unit. 
 
     
     
       26. The method of  claim 24 , wherein the polymerizing includes reacting the monomer unit with reagent for providing a linking group between first and second diborylene units derived from the monomer. 
     
     
       27. The method of  claim 24 , wherein the polymerizing includes reacting the monomer unit with at least one of an alkynl ditin compound and an aryl ditin compound. 
     
     
       28. The method of  claim 24 , further comprising end capping the polymer with a phenylacetylene. 
     
     
       29. An electronic device comprising:
 first and second electrodes; and an active layer which spaces the first and second electrodes, the active layer comprising a n-type conjugated compound comprising at least one cyclic diborylene unit, wherein the at least one cyclic diborylene unit includes two boron atoms in a same ring. 
 
     
     
       30. The electronic device of  claim 29 , wherein the active layer further includes an electron blocker. 
     
     
       31. The electronic device of  claim 29 , wherein the diborylene unit has the general structure represented by Structure 2: 
       
         
           
           
               
               
           
         
         wherein X and Y are independently selected from a π-conjugated group and a p-conjugated atom. 
       
     
     
       32. The electronic device of  claim 29 , wherein n-type conjugated compound contains only one diborylene unit.